Environ Geol DOI 10.

1007/s00254-007-0880-x

ORIGINAL ARTICLE

Assessment of organic pollutants in coastal sediments, UAE

Esam A. Abdel Gawad Mohamed Al Azab M. M. Lotfy

Received: 12 March 2007 / Accepted: 18 June 2007 Springer-Verlag 2007

Abstract Twenty-ve stations were selected along the UAE coastal region to delineate the distribution and to determine the source of total petroleum hydrocarbon (TPH), total organic carbon (TOC), total Kjeldhal nitrogen (TKN), polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). The concentrations of TPH ranged between 46 and 223 mg/kg and the level of TOC was in the range from 0.044 to 17.8 wt%, while TPAHs occupied the range of 5102.2 lg/kg. On the other hand, TPCBs showed values between 60 and 205 lg/kg and TKN ranged from 104 to 1,073 mg/kg. The present study shows that the distribution of organic compounds in UAE sediments were within safe limits comparing with previous studies. The present study revealed that TOC can be used as an indicator of oil pollution in heavily oiled sediments. The highest values of TOC, TPH, TPAHs and TPCBs related to the stations covered in ne sand due to adsorption properties and the large surface areas of the grains. The evaporation of low-boiling point compounds from surface layers leads to the enrichment of sediments with a thick residual. Al Sharjah-1 exhibited the highest values of TPH and TOC at Ras Al-Khaima-5, Umm AlQuwen-1 and Dubai-1, while the highest values of TPAHs were at KhorFakkan-9, the highest value of TPCBs was at Ajman-2, and the highest values of TKN were at KhorFakkan-1, KhorFakkan-6 and Dubai-1.

Keywords Pollution Organic TOC PAHs PCBS Hydrocarbons TKN UAE

Introduction The rapid development in the past 15 years in the Arabian Gulf region generally and in UAE specially has thrown a heavy burden on coastal zones and reects an adverse impact on coastal habitats. The petroleum industry, which is mostly concentrated on the coastal region, raises the level of oil and other organic compounds in marine sediments. In the past few years, the Dubai coastal zone was subjected to several developments, which have affected the water and sediment quality. According to Mocke et al. (2002), 20% of the study area is industrial, 16.5% private usage, 14% public usage and 15.5% Sanctuary (Jebel Ali). A periodic monitoring of petroleum hydrocarbon level in Gulf coastal countries is useful in estimating any change in water and sediment quality. Contamination by petroleum hydrocarbon is a serious problem throughout the world. An increase in petroleum hydrocarbons in the marine environments causes a negative impact not only on the aquatic life but also may be extend to affect human heath through interference in the food web and through contamination of seawater. A large percentage (>3050%) of spilled hydrocarbons enriched in heavier more recalcitrant compounds deposited in bottom sediments, beaches and soils which then act as long-term reservoirs and secondary sources (Colombo et al. 2005) Furthermore, one of their major economic impacts is the reducing the recreational utility of coastal waters. Oil in the sea, whether from spills or chronic sources, is perceived as a major environmental problem. Occasional major oil spills receive considerable public attention because of the obvi-

M. Al Azab Department of Chemistry, Faculty of Science, UAE University, P.O. Box 17551, Al-Ain, UAE E. A. Abdel Gawad M. M. Lotfy (&) Department of Geology, Faculty of Science, UAE University, P.O. Box 17551, Al-Ain, UAE e-mail: mostafa.lotfy@uaeu.ac.ae

123

Environ Geol

ous attendant environmental damage such as oil-coated shorelines, and dead or moribund wildlife, including, in particular, oiled seabirds and marine mammals (NAP 2003).

Table 1 Location for the collection of sediments Stations Location KH1 KH 2 KH 3 Stations Location Coastal-Ras Al-Khaimah Coastal-Ras Al-Khaimah Coastal-Ras Al-Khaimah Coastal-Ras Al-Khaimah Coastal-Umm-Al-Quwain Coastal-Umm-Al-Quwain Coastal-Umm-Al-Quwain Coastal-Ajman Coastal-Ajman Coastal-Sharjah Coastal-Sharjah Coastal-Dubai Coastal-Dubai

Coastal-KhorFakkan Ras1 Coastal-KhorFakkan Ras2 Coastal-KhorFakkan Ras3 Coastal-KhorFakkan Ras5 Coastal-Kalba Coastal-Kalba Coastal-Kalba Coastal-Kalba Coastal-Fujairah Coastal-Fujairah Coastal-Fujairah Coastal-Fujairah Qu1 Qu2 Qu3 Aj1 Aj2 Sh1 Sh2 Du1 Du2

Materials and methods Sample collection The stainless Van Veen grab sampler was used to obtain the sediments samples. Twenty-ve of bottoms offshore sediment within the depths of 1520 m was gathered (Fig. 1). Each fully mixed sample was air dried under a hood at room temperature and sieved to pass a 35-mesh sieve. The samples were kept frozen at 18C for the future analyses, the collection were started from Kalba, Fujairah, Khor Fakkan, Ras Al-Khaimah, Umm Al-Quwen, Ajman, Sharjah and of Dubai coastal region (Table 1). These samples were frozen in airtight plastic bags; all necessary precautions were taken to avoid any contamination or the loss of volatilize compounds. Analytical methods The sediments samples were dried in oven under mild temperature to remove the moisture before sieving. The textural class was determined through grain-size analysis by using standard set of sieves and mechanical shaker. The dry weight percentage of the size fractions retained on each sieve was calculated. For the muddy samples, which contains more than 20% mud, pipette analysis is the most common method used for determining the grain-size distribution of sediments >4u.

KH 4 KH 5 KH 6 KH 7 KH 8 KH 9 KH 10 KH 11 KH 12

55 o

56 0

Arabian Gulf
Ras Al-khaimah
Ras4 Ras1

26o

Umm Al-quwen
QU2 QU3 QU1 AJ1

Gulf of Oman
Khor Fakkan

Ajman Sharjah Dubai

DU2 0 20

Kh4

AJ2 Sh1 Sh2

Kh1

Fujairah
Kh12

United Arab Emirates

DU1 Kh5

25 o

Kalba
Locations

40

60 Km

Cities

Oman

Fig. 1 Location map of the studied sites in UAE

The concentration of total petroleum hydrocarbon (TPH) was measured in accordance as it is explained by ROPME (2000). From the homogenized, eld-moist sediment 20 g were extracted in a Soxhlet by using hexane solvent. TPH was determined by measuring the absorbance of uorescence using a Nicolet Infrared Spectrophotometer. The percentage weight of total organic carbon (TOC) was carried out by following the Walkey-Black (1947) method based on the oxidation of organic matter with concentrated Sulfuric acid and titration to the end point with ferrous ammonium sulfate. Total Kjeldhal nitrogen (TKN) was determined according to Kjeldahl method (EPA 1993) using block digestion and steam distillation. This method requires the digestion of the solid sample to solution using strong acid at high temperatures. The digestion tube was placed in the distillation unit and the distillate was titrated with standardized HCl acid. The quantication of polycyclic aromatic hydrocarbons (PAHs) were brought out through high performance liquid chromatography (HPLC) with a uorescence detector, the sample was dried with anhydrous sodium sulfate and extracted in a Soxhlet extraction using mixture of hexane: acetone (50:50) for 2 h boiling and rinsing. The extract was injected into HPLC column. Finally, the determination of polychlorinated biphenyl (PCB) was carried out using gas chromatography with an electron capture detector (GC-ECD). The sample was extracted in a Soxhlet extraction using solvent (1:1 hexane: acetone) for 2 h, the residual of the solvent after evaporation was collected and injected into GC-ECD column to recognize PCB compounds (EPA 1999). N-alkanes and isoprenoids hydrocarbons were determined by gas chromatography with a ame ionization detector (GC-FID) with the following specication and condition, Varine, Saturn 3800 GC system, equipped with am ionization, detector FID,

123

Environ Geol

GC column: CP-Sil 8, 30 m 0.32 mm ID, df = 1, Carrier Gas: He 1.5 ml/min, Temperature program of the oven 100160C at 15C/min for 2 min, followed by 160300C at 5C/min for 30 min. The detection limits of our analytical compounds have been done as reference material analysis by Al-Darwish et al. (2005) and Al katheeri (2004).

Table 2 Concentrations of TPH, TOC and TKN in UAE sediments Sample ID Kh1 Kh2 Kh3 Kh4 Kh5 Kh6 TPH (mg/kg) 86 134 163 199 157 119 156 140 101 141 126 93 128 74 91 97 82 54 134 125 152 223 64 76 46 TOC wt% 0.162 0.088 0.089 0.088 0.191 0.28 0.119 0.044 0.088 0.103 0.191 0.058 11.25 3.832 8.787 17.05 17.8 8.219 12.33 11.88 3.46 5.548 3.985 17.05 14.59 TKN (mg/kg) 305 104 132 116 nd 286 104 nd nd nd nd nd nd nd 108 nd 1,073 nd nd nd nd nd nd 239 nd

Results and discussion Sediments distribution The objectives of determining the grain-size distribution of sediments in this study is to correlate the level of contaminants to grain size, and to determine the texture of the sediments, i.e., the percentage of ne particles in the sediment. The coarse sandy sediments are mainly restricted to the southern regions of the Gulf, and the ne clay silt sediments are mainly concentrated in the northern regions (Al-Ghadban et al. 1996). The textural classes in the Gulf of Oman area fall into four main groups: ne sand, medium sand, coarse sand, and pebble (Fig. 2a). The textural classes in the Arabian Gulf area also fall in ve other groups: ne sand, medium sand, coarse sand, very coarse sand and granule (Fig. 2b). Most of the study area (36%) is medium sand, while the ne size deposits represent (24%), coarse sand represent (16%), very coarse sand (12%), pebble (4%) and granule (8%). Content of TPH, TOC and TKN Chronic releases from natural and anthropogenic sources (e.g., natural seeps and run-off from land-based sources) are responsible for majority of petroleum hydrocarbon input (NAP 2003). Typically, petroleum hydrocarbon concentrations are a few mg/kg in unpolluted coastal areas and from 50 to more than 1,000 mg/kg in polluted areas (Clark and Macleod 1977). The values of TPH in UAE sediments show drastic uctuations, varying from 46 to 223 mg/kg, with an average of 118.44 43.67 (see Table 2). It is

Kh7 Kh8 Kh9 Kh10 Kh11 Kh12 Ras1 Ras2 Ras3 Ras5 Qu1 Qu2 Qu3 Aj1 Aj2 Sh1 Sh2 Du1 Du2

Average SD 118.44 43.668 5.49128 6.440 98.68 223.979 nd not detected

worth to noting that Sharjah-1and KhorFakkan-4 showed high levels of TPH (223 mg/kg and 199 mg/kg, respectively), whereas other locations showed only slight and moderate levels of TPH. These locations showed very high concentrations of TPH compared with the obtained values from the Gulf region after the 1991 Gulf War. For example, Massoud et al. (1996) found TPH in heavily polluted areas affected by the Kuwait oil slick ranged from 266 to 1,448 mg/kg. Hayes et al. (1993) reported that the con-

Fig. 2 Textural classes of sediments (a) gulf of Oman and (b) Arabian Gulf in UAE

Mean size

B
Fine sand Medium sand

Mean size

Fine sand Medium sand Coarse sand Pebble

Coarse sand Very coarse sand Granule

123

Environ Geol

centrations of TPH in sediments at the most severely impacted locations along the Saudi Arabian coast one year after the Gulf War oil spill were 10,000 mg/kg. The high level of TPH at Sharjah-1 and KhorFakkan-4 as well as Ajman-2 (Fig. 3a) could be attributed to its location close to Sharjah Port, which is used for oil exporting. In addition, other resources could be navigation routes, tanker transport and coastal production, which is other sources of oil pollution in the region (Golob and Brus 1984). The distribution map (Fig. 3b) of TPH demonstrates unusual levels of THP at Sharjah-1, Khorfakkan-4 and Ajman-2, which may have occurred as a temporal event during or shortly before the period of samples collection. The moderate concen-

TPH mg/kg

A
Concentration mg/kg

250

200

150

100

50

0 Kh1 Kh2 Kh3 Kh4 Kh5 Kh6 Kh7 Kh8 Kh9 Kh10 Kh11 Kh12 Sh1 Sh2 Ras 1 Ras 2 Ras 3 Ras 5 Ag1 Ag2 Du1 Du2 Q u1 Q u2 Q u3

Stations
TOC wt%

B
Toc wt %

20 18 16 14 12 10 8 6 4 2 0 Du2 Ras 1 Ras 2 Ras 3 Ras 5 Q u1 Kh11 Kh12 Kh10 Q u2 Q u3 Du1 Kh1 Kh2 Kh3 Kh4 Kh5 Kh6 Kh8 Kh7 Kh9 Sh1 Sh2
Aj1 Aj2

Stations

C
Concentration mg/kg

TKN (mgN/Kg)
1200 1000 800 600 400 200 0 Ras 1 Ras 2 Ras 5 Aj1 Kh11 Kh10 Kh12 Ras 3 Q u3 Q u1 Q u2 Kh4 Kh5 Kh7 Kh2 Kh3 Kh6 Kh8 Kh1 Sh1 Sh2 Kh9 Du1 Du2 Aj2

Stations

Fig. 3 Distribution of TPH (a), TOC (b) and TKN (c) in UAE sediments

tration of TPH at Dubai-1and Dubai-2 is mostly attributed to the presence of dry docks, which might received petroleum input from damaged tankers, water depilating and tanker maintenance, whereas the source of oil input at the other stations referred to is most likely from private usage of coastal zone. On the other hand, the high level of TPH at the Arabian Gulf coastal could also be as a result of the movement of surface waters with high oil contents form the Gulf of Oman through the Strait of Hormuz (Shriadah 1998). The input of organic matter to coastal systems is, indeed, the triggering mechanism leading to the ecological consequences of concern (DellAnno et al. 2002). TOC value indicates the sum of organic carbon and represents a measure for all organic substances in sediments. These substances are from (1) natural sources, such as humic acids, mineral oils, solvents, pesticides, and polyaromatic hydrocarbons or (2) chlorinated organic compounds. The values of TOC ranged from 0.044 to 17.8 wt% with an average of 5.49 6.44. Hartmann et al. (1971) pointed out that the sediments of the Arabian Gulf generally contain between 0.5 and 1.0 wt%, or at the most 2.0%. Literathy et al. (1992) reached the previous nding on the natural background levels of TOC (0.50.8 wt%) in the bottom sediments of Kuwait marine environment. Table 3 illustrates the concentrations of TOC along UAE coast, which have been reported by several researchers from 1992 to 2003. TOC in UAE sediments (Fig. 3b) shows high levels for the western region sediments compared with the eastern western partregion sediments. The real distribution of TOC (Fig. 4b) exhibits that the western part shows higher levels of TOC compared with other eastern part which shows lower levels of TOC in UAE sediments. Table 3 displays discordance in the distribution of petroleum hydrocarbons and the percentage of organic matter in sediments. This nding is conrmed by signicant negative correlation (r = 0.423) between TPH and TOC, which shows disagreement with earlier ndings of Shriadah (1998), who found that of organic carbon in the sediments, the greatest was the adsorption of petroleum hydrocarbons. Therefore, it may be suggested that the percentage of TOC could be used as an indicator of petroleum pollution in the area; this conclusion is in agreement with the earlier observations of Emara (1998). Ammonication refers to the way some organisms x nitrogen to either NH+ 4 or organic nitrogen (nitrogen xation); nitrication refers to organisms that nitrify NH+ 4 to NO3. Both nitrication and ammonication convert gaseous nitrogen into bioavailable chemical forms (Wilson et al. 1993). TKN stands for total Kjeldahl nitrogen, which is the sum of ammonia (NH3) and organic nitrogen. According to measurement of TKN in UAE sediments, the values showed very wide variation, ranging from 0 to

123

Environ Geol Table 3 Compared total organic carbon contents (TOC wt%) in sediments from the UAE coasts Reference Abu-Hilal and Khordagui (1992) Abu-Hilal and Khordagui (1992) Abu-Hilal and Khordagui (1992) Shriadah (1998) Shriadah (1998) Shriadah (1998) Shriadah (1998) El-Sammak (1998) Al-Qubaisi (2001) Deshgooni (2002) Al Katheeri (2004) Tolosa et al. (2005) Al-Darwish et al. (2005) Present study Journal title The Arabian Gulf and Gulf of Oman. Annual report The Arabian Gulf and Gulf of Oman. Annual report The Arabian Gulf and Gulf of Oman. Annual report Indian Journal of Marine Sciences Indian Journal of Marine Sciences Indian Journal of Marine Sciences Indian Journal of Marine Sciences Regional conference on the marine environment of the Gulf Master science Thesis UAEU Master science Thesis UAEU Master science Thesis UAEU Marine Pollution Bulletin Environmental Geology Environmental Geology Area Dubai Sharjah Ajman Ras Al-Khaimah, Umm Al-Quwain Sharjah Abu Dhabi Dubai Creek Dubai Dubai Creek Abu Dhabi Gulf of Oman Dubai offshore UAE Range 0.142.65 0.441.36 0.241.42 0.120.89 0.150.38 0.491.2 0.450.77 0.00520.445 0.060.27 0.35.8 0.1414.96 0.11.53 0.165.9 0.08817.8 Average SD 1.02 1.15 0.78 0.35 0.7 0.5 0.34 0.29 0.27 0.22 0.57 0.43 0.61 0.4 0.153 0.1 0.08 2.7 1.6 4.77 3.70 0.443 0.5452 0.86 1.44 5.49128 6.440

1,073 mg/kg, with an overall average of 98.68 223.98 (Table 2) at KhorFakkan-1, KhorFakkan-6 and Dubai-1. The level of TKN suggested by Alloway (1993) in coastal sediments is 300 mg/kg. The high concentrations of TKN are probably originated from run-off of fertilizers, livestock and human wastes and municipal sewage-treatment facilities. This indicates coastal discharges or may be attributed to high levels of TPH (223 mg/kg), which increases the mortality rate among the aquatic organisms such as phytoplankton and zooplankton that in turn enhances the bacterial decomposition activity, which increases the rate of nitrite. The signicant negative correlation (r = 0.175) between TKN and TPH did not conrm the bacterial decomposition. According to the measurements of TKN in UAE sediments, the values showed wide variations within the range of 01,073 mg/kg (Fig. 3c). Figure 4c illustrates the distribution trend of TKN in UAE sediments the high level of TKN (305 mg/kg) KhorFakan-1, which has moderately value of TPH (86 mg/kg), majority attributed to highly terrestrial input (El-Sabrouti et al. 1990). Content of TPAHs and TPCBs Polycyclic aromatic hydrocarbons are a class of organic pollutants that are released into the environment in large quantities, mainly due to human activities. There are two primary sources of PAHs to the marine environment, pyrogenic and petrogenic: pyrogenic PAHs are derived from combustion sources and petrogenic PAHs are derived from petroleum inputs. In UAE sediments, TPAHs values uctuated between 5 and 102.5 mg/kg with an average of 30.64 23.59 (Table 4, Fig. 5a). The distribution map of TPAHs exhibits increasing trends in the western sediments

rather than the eastern ones (Fig. 6a). The maximum value was reported at KhorFakan 9. The primary source of anthropogenic PAHs in the environment is thought to be atmospheric depositions (Witt 1995). TPAHs in UAE sediments found to be lower than the values recorded along the Saudi Arabian coast (10300 lg g1) 1 year after the Gulf War (Hayes et al. 1993), in heavily oil contaminated sediments. However, the level is still high compared with other regions in the world. This conrms the earlier conclusion proposed by Evans et al. (1990) that the highest amount of PAHs is usually associated with sediments that have a high TOC. The distribution pattern appeared to be related to oil pollutant sources, such as discharge from vessels and port activities (Hong et al. 1995). Polychlorinated biphenyls are now widespread in the environment and can be detected in air, water, soil, sediments and organisms; the typical environmental concentration is 2 50 lg kg1 in soil (Killops and Killops 1993). PCBs tend to adsorb to ne particulates or be bio accumulated into lipids in aquatic biota (Olsen et al. 1982). According to Fang et al. 2003 phenanthrene/anthracene (P/A) ratio is equal to 1 for coastal sediment samples within the study area, except for station KH7 (0.9), which reects pyrogenic sources of PAHs benzo(a)anthracene/(benzo(a) anthracene + chrysene stations KH4, KH7, KH8, KH9, and KH10 have values of BaA/(BaA + Chry) 0.4 which reects petrogenic sources, while stations KH1, KH2, KH3, KH5, KH6, KH11, and KH12 attain the values of BaA/ (BaA + Chry) ranging from 0.5 to 0.75, indicating pyrogenic sources. According to Guinan (2001) uoranthene/ (uoranthene + pyrene) ratio Flu/(Flu + P) > 1 indicates pyrogenic sources while values <1 indicate petrogenic sources of PAHs. Within the study area, the Flu/(Flu + P)

123

Environ Geol
56 0

55 o

Table 4 Concentrations of TPAHs and TPCBs in Dubai sediments Sample ID TPCBs (mg/kg) 115 95 140 130 80 140 80 105 75 125 90 75 70 95 110 75 110 90 110 180 205 95 60 90 75 104.6 34.367 TPAHS (mg/kg) 49.9 27.5 52.9 36.4 62.6 16.5 50.9 40.7 102.2 13.5 11.6 24.4 14.2 17.9 42.9 26.4 10.7 28.4 11 5 5 13.8 22 11 68.7 30.644 23.590

Arabian Gulf
Ras Al-khaimah
Ras4 Ras1

26o

Kh1 Kh2 Kh3 Kh4 Kh5 Kh6 Kh7 Kh8

Umm Al-quwen
QU2 QU3 QU1 AJ1

Gulf of Oman
Khor Fakkan

Ajman Sharjah Dubai

DU2 0 20

Kh4

AJ2 Sh1 Sh2

Kh1

Fujairah
Kh12

United Arab Emirates

DU1 Kh5

25 o

Kalba
Locations

Kh9 Kh10 Kh11 Kh12 Ras2 Ras3 Ras5 Ras1 Qu1 Qu2 Qu3 Ag1 Ag2 Sh1

40

60 Km

Cities

Oman

o 55

0 56

Arabian Gulf
Ras Al-khaimah
Ras4 Ras1

o 26

Umm Al-quwen
QU2 QU3 QU1 AJ1

Gulf of Oman
Khor Fakkan

Ajman Sharjah Dubai

DU2 0 20

Kh4

AJ2 Sh1 Sh2

Kh1

Fujairah
Kh12

United Arab Emirates

DU1 Kh5

25o

Sh2 Du1 Du2 Average S.D

Kalba
Locations

40

60 Km

Cities

Oman

55 o

56 0

Arabian Gulf
Ras Al-khaimah
Ras4 Ras1

26o

Umm Al-quwen
QU2 QU3 QU1 AJ1

Gulf of Oman
Khor Fakkan

Ajman Sharjah Dubai

DU2 0 20

Kh4

AJ2 Sh1 Sh2

Kh1

Fujairah
Kh12

United Arab Emirates

DU1 Kh5

25 o

Kalba
Locations

40

60 Km

Cities

Oman

Fig. 4 Distribution maps of TPH (a), TOC (b) and TKN (c) in UAE sediments

On the basis of all the above-calculated ratios, it can be concluded that sources of pollution within the study area are predominantly of petrogenic origin (oil spill), in addition to minor contribution from pyrogenic sources (combustion of oil products and shipping activities at nearest harbor). TPCBs in UAE sediments values ranged from 60 to 205 lg/kg. The maximum value was reported at Ajman 2, with an average of 104.6 34.38 (Table 4, Fig. 5b). Figure 6b represent the distribution map of TPCBS towards the western region where the maximum value is about three times higher than the minimum. Ajman-2 represents four times higher than the typical environmental concentration. However, both PCBs and PAHs showed the maximum value at KhorFakan-9 and Ajman-2, respectively, but PCBs exhibit wider range of distribution in the study area (Fig. 7). Hydrocarbons Hydrocarbons from both anthropogenic and natural sources including biogenic sources are very common in the

ratio was ranging from 0 at KH1, KH6 and KH12 to 1 at KH2, KH3 and KH8 for coastal sediments. The concentration at most stations was less than 1, indicating petrogenic sources of PAHs.

123

Environ Geol
TPAHs mg/Kg
120 100
56 0

A
C oncentration mg/Kg

55 o

80 60 40 20

Arabian Gulf
Ras Al-khaimah
Ras4 Ras1

26o

Umm Al-quwen
QU2 QU3 QU1 AJ1

Gulf of Oman
Khor Fakkan

Ajman
0
k h1 k h3 k h4 k h8 k h9 k h2 Ras 2 k h5 k h7 k h10 Ras 3 k h6 k h11 Ras 5 k h12 Ras 1 Du1 Du2 s h2 s h1 Aj1 Aj2

Kh4

Sharjah Dubai

AJ2 Sh1 Sh2

Kh1

Fujairah
Kh12

Stations
DU1

United Arab Emirates

Kh5

25 o

Kalba
Locations

B
C oncentration mg/K g

250

TPCBs mg/Kg

DU2 0 20 40 60 Km

Cities

200
55 o

Oman

150

56 0

100

Arabian Gulf
50

26o Ras4 Ras1

Ras Al-khaimah

0
KH1 KH2 KH3 KH4 KH5 KH7 KH8 KH6 KH9 KH11 KH12 Q u1 KH10 Sh2 Ras 1 Ras 3 Ras 5 Aj1 Q u2 Ras 2 Q u3 Sh1 Du1 Du2 Aj2

Umm Al-quwen
QU2 QU3 QU1 AJ1

Gulf of Oman
Khor Fakkan

Stations

Ajman Sharjah Dubai

Kh4

Fig. 5 Distribution of TPAHs (a) and TPCBs (b)

AJ2 Sh1 Sh2

Kh1

Fujairah
Kh12

United Arab Emirates

DU1 Kh5

25 o

marine and inland environments. Biogenic hydrocarbons are generated either by biological processes or in the early stages of diagnosis in recent marine sediments. Biological sources include land plants, phytoplankton, animals, bacteria, macroalgae and microalgae. Stated that the distinct characteristics of biogenic hydrocarbons including a much higher abundance of odd n-alkanes is a wide range between n-C21 to n-C33 and high CPI and pristane/phytane values. It has been recognized in the studied coastal sediments in UAE that the biogenic hydrocarbons have the following chemical composition characteristics: (1) n-alkanes show a distribution pattern of odd carbonnumbered alkanes being much abundant than even carbon-numbered alkanes in the range of n-C 21 to n-C33, resulting in unusually high carbon preference index (CPI) values, which is dened as the sum of the odd carbonnumbered alkanes to the sum of the even carbon-numbered alkanes (oils characteristically have CPI values around 1.0); (2) A notable absence of the unresolved complex mixture (UCM) hump in the chromatograms; (3) pristane is often more abundant than phytane, suggesting a phytoplankton input and resulting in abnormally high pristane/phytane ratio values in most studied locations (Fig. 8av). In the study of the hydrocarbon biogeochemical setting of coastal sediments in the UAE, we found that very high pristane/phytane ratios (0.494.48)

Kalba
Locations

DU2 0 20 40 60 Km

Cities

Oman

Fig. 6 Distribution map of TPAHs (a) and TPCBs (b) in UAE sediments

250

TPAH&TPCBs mg/Kg

Concentration mg/Kg

200

150

100

50

0 Kh1 Kh2 Kh3 Kh4 Kh5 Kh6 Kh7 Kh8 Kh9 Kh10 Kh11 Kh12 Ras 2 Ras 3 Ras 5 Ras 1 Q u1 Q u2 Q u3 Ag1 Ag2 Sh1 Sh2 Du1 Du2

Station

Fig. 7 Comparison between the distribution of TPAHs and TPCBs in UAE sediments

123

Environ Geol

and CPI values (0.751.33). The CPI has been a useful parameter for estimating biogenic or anthropogenic contributions since it was rst put forward. The n-alkanes from higher plants waxes show a pronounced odd carbon number preference, while fossil fuel and microbial

hydrocarbons exhibit CPI  1. The carbon number ranges used for calculations are different among different researchers. In the present study, the CPI for n-alkanes was calculated as follows: CPI1 (whole range for n-alkanes) = R(C13C35)/R(C14C36); CPI2 (petrogenic n-

7 6

kh1

kh 2

Concentration

Concentration

5 4 3 2 1 0 C13 C15 C16 C18 C19 C21 C23 C25 C27 C29 C31 C33 C35 C37 C39

4 3 2 1 0
C13 C15 C16 C18 C19 C21 C23 C25 C27 C29 C31 C33 C35 C37 C37 C37 C37 C39 C39 C39 C39

Carbon number
14
4

Carbone number

12

kh3

kh4

Concentration

Concentration

10 8 6 4 2 0

C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39

Carbon number
5

Carbon number

12
4 4

kh5
10

C35 C35 C35

kh6

Concentration

3 3 2 2 1 1 0

Concentration
C13 C15 C16 C18 C19 C21 C23 C25 C27 C29 C31 C33 C35 C37 C39

C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

Carbon number
7.00 6.00
1.2

Carbon number

kh7
Concentration

C33 C33

1.0 0.8 0.6 0.4 0.2 0.0

C13 C15 C16 C18 C19 C21 C23 C25 C27 C29

Concentration

kh8

5.00 4.00 3.00 2.00 1.00 0.00

C13 C15 C16 C18 C19 C21 C23 C25 C27 C29 C31 C33 C35 C37 C39

Carbon number

Carbon number

Fig. 8 Distribution of n-alkanes in the offshore sediments in UAE

123

C31

Environ Geol
12

12

kh9
10

10

kh10

Concentration

Concentration
C 13 C 16 C 19 C 23 C 31 C 33 C 18 C 27 C 29 C 35 C 15 C 21 C 25 C 37 C 39

8 6 4 2 0
C 35 C 37 C 16 C 19 C 21 C 25 C 13

Carbon number
10

Carbon number
14.0

9 8

kh11
12.0

C 23

C 27

C 15

C 18

C 29

C 31

C 33

kh12

Concentration

7 6 5 4 3 2 1

Concentration

10.0 8.0 6.0 4.0 2.0 0.0 C 15 C 18 C 19 C 29 C 21 C 35 C 25 C 31 C 16

C 13

C 15

C 16

C 18

C 19

C 21

C 23

C 25

C 27

C 29

C 31

C 33

C 35

C 37

C 39

Carbon number
30
0.40 0.35

Carbon number

C 23

AJ-1

25

AJ-2

Concentration

0.30 0.25 0.20 0.15 0.10 0.05 0.00 C15 C16 C18 C19 C21 C23 C25 C27 C13 C29 C31 C35 C37 C33 C39

Concentration

20

15 10

5 0 C15 C19 C13 C21 C16 C18 C23 C33 C25 C29 C31 C35 C27 C37
C 39

C 37

C 39

C 13

C 27

C 33

C 39

Carbon number
24
12

Carbon number

20

QU-1
10

QU-2

Concentration

16

Concentration

12

0 C 19 C 16 C 23 C 35 C 13 C 37 C 25 C 29 C 18 C 27 C 31 C 33 C 39 C 15 C 21

0 C 15 C 19 C 21 C 23 C 25 C 16 C 18 C 27 C 29 C 31 C 13 C 33 C 35 C 37

Carbon number

Carbon number

Fig. 8 continued

alkanes) = R(C13C23)/R(C14C24), and CPI3 (higher plant wax n-alkanes) = R(C25C35)/R(C26C36) (Zhu and Wang 2004). Within the study area, the CPI1 of coastal sediments samples was ranging from 0.89 to 1.35 reecting similar petrogenic sources of pollution rather than biogenic. The CPI2 for the coastal sediment samples

was ranging from 0 to 0.89. Thus, most CPI2 values were closed to 1 indicating petrogenic sources rather than biogenic sources. Finally, CPI3 values ranging from 0.8 to 1.4 for coastal sediments, suggesting higher plants waxes as the predominant source for the obtained n-alkanes range of the studied samples.

C39

123

Environ Geol
14 12

20

QU3
Concentration
15

DU-1

Concentration

10 8 6 4 2 0
C15 C16 C18 C19 C21 C23 C25 C27 C29 C31 C33 C35 C13 C37 C39

10

0
C13 C15 C16 C18 C19 C21 C23 C25 C27 C29 C31 C33 C35 C37 C37 C37 C39 C39 C39

Carbon number
10 9 8

Carbon number
12

SH-1

10

SH-2

Concentration

7 6 5 4 3 2 1 0

Concentration
C13 C15 C16 C18 C19 C21 C23 C25 C27 C29 C31 C33 C35 C37 C39

C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33 C33

Carbon number
25

Carbon number
14 12

20

Rase 2

Concentration

Concentration

15

Rase 1

10 8 6 4 2

10

0
C13 C15 C16 C18 C19 C21 C23 C25 C27 C29 C31 C33 C35 C37 C39

0
C13 C15 C16 C18 C19 C21 C23 C25 C27 C29 C31

Carbon number

Carbon number

Fig. 8 continued
1.0
PCBS

FACTOR(2)

High concentrations of pristane relative to phytane in most coastal sediments indicate biological hydrocarbon input from a marine biological source (planktonic or bacterial origin). Factor analysis The principal component factor analysis, at its simplest, can be regarded as an ordination technique for reducing multivariate data into fewer dimensions (Rock 1988). Factor analysis was applied for selected elements and compounds. The analysis reveals two factor solutions (Fig. 9a, b). Organic compounds (TOC, TPH, TKN, and Tpcbs) are positively loaded on factor 1 and may be termed the pollution factor. The second factor is represented by TPAHs. In the computation of correlation between TOC, TPH, TPAHs, TKN, and TPCBs (Fig. 10a, b, Table 5)

0.5
TKN TOC

C35

C35

TPH

0.0

-0.5
PAHS

-1.0 -1.0

-0.5

0.0

0.5

1.0

FACTOR(1)

Fig. 9 Factor analysis

from the regression analysis, TOC correlated signicantly positive with TKN (r = 0.504) and there was a positive correlation between TPH and TPCBs (r = 0.366; Fig. 11).

123

Environ Geol Fig. 10 Scatter plot showing the relationship between TKN and TPH (a), TOC and TPH (b), TOC and TPAHs, and (c) TOC and TKN (d)

A 1200
1000

250 200

TKN mg/Kg

TOC wt%

800 600 400 200 0

150 100 50 0

50

100

150

200

250

10

15

20

TPHmg/Kg

TPH mg/Kg

20

D 1200
1000 800 600 400

15

TOC wt%

10

5 200 0 0

20

40

60

80

100

120

TOC wt%

10

15

20

TPAHs mg/Kg

TKN mg/Kg

Table 5 Correlation factor between TPH, TKN, TOC, TPAHs and Tpcbs in offshore sediments at UAE Correlation factor TPH PCBS TKN PAHS TOC TPH PCBS TKN PAHS TOC

Conclusions The analyses of the coastal sediments in UAE indicate the following: 1. Association of the high TPH and TOC values with the lithogenic metals rather than man-made conrms the biogenic origin for the hydrocarbons. The coastal sediments in UAE can be categorized into two groups, the biogenic cluster was obvious and no UCM was observed. It has been recognized that hydrocarbons from natural sources including biogenic source are very common in the inland environments. The coastal sediments showed typical biogenic n-alkane distribution ranging form C21 to C33 with abundance of odd-carbon number n-alkanes being much higher than that of even-carbon number n-alkanes. TPH showed a wide distribution in the study area and that is mainly attributed to the nature of the region and the production and transport of petroleum. Al Sharjah-1 represents the most contaminated part in the study area and the major source of contamination is attributed to anthropogenic sources. The presence of Al Sharjah Port in the eastern part of the study area provides a reasonable source of the high level of contamination. The ne and poorly sorted sand tend to have high values of organic substance and heavy metals. The adsorption onto ne-grained sediments is probably due to the larger surface area.

1.000 0.366 0.175 0.062 0.139 1.000 0.101 0.345 0.221 1.000 0.160 0.504 1.000 0.225 1.000

2.

3.
TOC PAHS PCBS TPH

4.

5.
TKN
0 50 100 150 200 250

6.

Fig. 11 Cluster analysis of TPH, TOC%, TKN, total PAH and total PCBs associations in offshore sediments at UAE

Figure 11 illustrates that the organic pollutants could be classied into two main groups: (a) TPH, PCBs, PAHs and TOC, which represent hydrocarbon pollution and (b) TKN, which represents the main man-made pollution, which probably originated from run-off of fertilizers, livestock and human wastes and municipal sewage-treatment facilities.

7.

123

Environ Geol

8.

The variation in concentrations from one site to another, the high relative standard deviation of most studied pollutants and the high levels of these pollutants in the developed areas compared with the rural suggest anthropogenic sources. Also the distance from the coastal zone can be considered as a controlling factor of concentration and distribution of pollutants.

Acknowledgments Authors thank the Central Laboratory Unit (CLU) and Petroleum Geochemistry Laboratory in the United Arab Emirates for the analysis of the samples.

References
Abu-Hilal A, Khordagui HK (1992) Heavy metals in creeks and near shore sediments of the United Arab Emirates: The Arabian Gulf and Gulf of Oman. Annual report. Desert and Marine Environment Research Center, Al-Ain, UAE Al-Darwish HA, Abd El-Gawad EA, Mohammed FH, Lotfy MM (2005) Assessment of contaminats in Dubai coastal region, UAE. Environ J 49:240250 Al-Ghadban A, Massoud M, Al-Abdali F (1996) Bottom sediment of the Arabian Gulf: I. Sedimentological characteristics. Kuwait J Sci Eng 23:7188 Al Katheeri BS (2004) Geochemical studies to assess marine oil pollution Zakum eld, Abu Dhaabai, UAE, M.Sc. Thesis, UAE University, pp 1108 Alloway BJ (1993) Chemical principles of environmental pollution. Blackee Academic and professional, an important of Chapman and Hall, London Al-Qubaisi NM (2001) Assessment of metals pollution in sediments of the coastal Area, UAE. MSc Thesis, UAE University, pp 1134 Clark RC, Macleod WD Jr (1977) Inputs, transport mechanisms, and observed concentrations of petroleum in the marine environment. In: Malins DC (ed) Effects of petroleum in artic and subarctic marine environments and organisms, vol 1. Academic, New York Colombo JC, Barreda A, Bilos C, Cappeleetti N, Migoya MC, Skorupka C (2005) Oil spill in the Rio de la Plata estuary, Argentina: 2-hydrocarbon disappearance rates in sediments and soils. Environ Pollut 134:267276 DellAnno A, Mei ML, Pusceddu A, Danovaro R (2002) Assessing the trophic state and eutrophication of coastal marine systems: a new approach based on the biochemical Composition of sediment organic matter. Mar Pollut Bull 44:611622 Deshgooni MA (2002) Modeling and assessment of environmental capacity, Dubai coastal region, United Arab Emirates. MSc. Thesis, UAE University, pp 1115 El-Sabrouti MA, Dowidar NM, El-Sammak AA (1990) Distribution of organic carbon, nitrogen and phosphorus in recent sediments of the Mediterranean Continental Shelf of Egypt. Acta Adriat 31(1/2):2335 El-Sammak A (1998) Geochemical model and normalization for heavy metals in the bottom sediments, Dubai, UAE. Regional Conference on the marine environment of the Gulf, 1215 December 1998. University of Qatar, Doha, p 112 Emara HI (1998) Total organic carbon content in the waters of the Arabian Gulf (Abstract). Environ Int 24:97103 EPA (Environment Protection Agency) (1993) the determination of nitrogen according to Kjeldahl using block digestion and steam distillation. A 300

EAP (Environmental Protection Agency) (1999) Polychlorinated biphenyls (PCBs) update: impact on sh advisories. EPA-823-F99-019 Evans KM, Gill RA, Robotham PWJ (1990) The PAH and organic content of sediment particle size fractions. Wat Air Soil Pollut 51:1331 Golob R, Brus E (1984) UNEP Reg Seas Rep Stud, vol 44, p 7 Guinan J (2001) Sources and geochemical constraints of polycyclic aromatic hydrocarbons (PAHs) in sediments and mussels of two northern Irish Sea-Loughs. Mar Pollut Bull 42:10731081 Fang MD, Lee CL, Yu CS (2003) Distribution and source recognition of polycyclic aromatic hydrocarbons in the sediments of Hsin-Ta Harbor and adjacent coastal areas, Taiwan. Mar Pollut Bull 46:941953 Hartmann M, Lange H, Seibold E, Walger E (1971) Oberachensedimente in Persian Golf und Golf von Oman. GeolgischHydologische Rohmen und erste sedimentologische Ergebnisse. Meteor Forsch 4:1.76 Hayes MO, Michel J, Montello TM, Aurand DV, Al-Mansi AM, AlMoamen A, Sauer TC, Thayer GW (1993) Distribution and weathering of shoreline oil one year after the Gulf War oil spill. Mar Pollut Bull 27:135142 Hong H, XU L, Zhang L, Chen JC, Wong YS, Wan TSM (1995) Environmental fate and chemistry of organic pollutants in the sediment of Xiamenand Victoria Harbours. Mar Pollut Bull 31:229236 Killops SD, Killops VJ (1993) An introduction to organic geochemistry. Longman Scientic and Technical, London Literathy P, Morel G, Zorba M, Samhan O, Al-Bloushi A, Al-Hashash N, Al-Matrouk K, Jacob PG (1992) Petroleum compounds in the marine environment of Kuwait. EES-100 Final Report, Kuwait Institute for Scientic Research, Kuwait Massoud MS, Al-Abdali F, Al-Ghadban AN, Al-Sarawi M (1996) Bottom sediments of the Arabian Gulf-II. TPH and TOC contents as indicators of oil pollution and implications for the effect and fate of the Kuwait oil slick. Environ Pollut 93:271284 Mocke GP, Smit F, Al Zahed K, Al Shaibani A (2002) Quantifying the coastal sedimentary processes of Dubai. General Projects Department, Dubai Municipality NAP (National Academy Press) (2003) Oil in the Sea III: inputs, fates, and effects. National Academy of Sciences, Washington Olsen CR, Cutshall NH, Larsen IL (1982) Pollutant-particle associations and dynamics in coastal marine environments: a review. Mar Chem 11:501533 Rock NMS (1988) Numerical geology, lecture notes in earth science, vol 18, Springer, Berlin, p 427 ROPME (2000) Regional organization of Protection for the Marine Environment, Kuwait Shriadah MMA (1998) Petroleum hydrocarbons along the Arabian Gulf coast of United Arab Emirates. Indian J Mar Sci 28:1016 Tolosa I, de Mora SJ, Fowler SW, Villeneuve JP, Bartocci J, Cattini C (2005) Aliphatic and aromatic hydrocarbons in marine biota and coastal sediments from the Gulf and the Gulf of Oman. Mar Pollut Bull 50(12):16191633 Walkey A (1947) A critical examination of a rapid method for determining organic carbon in soil. Soil Sci 63:251263 Witt G (1995) Polycyclic aromatic hydrocarbons in water and sediment of the Baltic Sea. Mar Pollut Bull 31:237248 Wilson HM, Gibson MT, OSullivan PE (1993) Analysis of current policies and policies and alternative strategies for the reduction of nutrient loads on eutrophication lakes: the example of Slapton Ley, Devon, aquatic conservation. Mar Freshw Ecosyst 3:239251 Zhu L, Wang J (2004) Pattern and sources of PAHs pollution in sediment of Hangzhou, China. Organohalogen compd 66:291 296

123